2-Stilbenyl-4-styryl-v-triazoles, their use for the optical brightening of organic materials, and processes for their manufacture

ABSTRACT

The present invention relates to detergents containing 0.001 to 0.5% by weight of new v-triazoles of the formula   WHEREIN X1 denotes hydrogen, halogen, methyl or optionally substituted phenyl, R1 denotes hydrogen, halogen, alkyl with 1 to 4 carbon atoms, optionally substituted phenyl or alkoxy with 1 to 4 carbon atoms, or together with R2 in the o-position denotes a fused benzene ring, R2 denotes hydrogen, halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, or together with R1 in the o-position denotes a fused benzene ring, R3 denotes hydrogen, a nitrile group, an optionally functionally modified sulpho group or an optionally functionally modified carboxyl group, R4 denotes hydrogen, halogen, a nitrile group, alkyl with 1 to 4 carbon atoms, optionally substituted phenyl, alkoxy with 1 to 4 carbon atoms, optionally functionally modified carboxyl or an optionally functionally modified sulpho group and R5 denotes hydrogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms. The detergent compositions can be used for brightening textiles.

United States Patent 1 Kabas et a1.

[ 1 Dec. 2, 1975 [75] Inventors: Guglielmo Kabas, Binningen; Hans Schlaepfer, Basel; Ian John Fletcher, Muenchenstein, all of Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed; Oct. 24, 1974' [21] Appl. N0.: 517,697

Related US. Application Data [62] Division of Ser. No. 237,204, March 22, 1972, Pat.

[30] Foreign Application Priority Data Mar. 31, 1971 Switzerland 4702/71 [52] U.S. Cl 252/89; 252/3012 [51] Int. Cl. CllD 3/42 [58] Field of Search 252/89, 301.2 W;

[56] References Cited UNITED STATES PATENTS 3,453,268 7/1969 Dorlars et a1. 260/240 3,511,834 5/1970 Siegrist et al. 260/240 3,579,511 5/1971 Weber et al. 260/240 3,642,783 2/1972 Siegrist et al. 260/240 3,689,429 9/1972 Duebel et al 252/3012 W Primary Examiner-William E. Schulz Attorney, Agent, or Firm-Joseph G. Kolodny; Edward McC. Roberts; Prabodh 1. Almaula [57] ABSTRACT The present invention relates to detergents containing 0.001 to 0.5% by weight of new v-triazoles of the formula wherein X denotes hydrogen, halogen, methyl or optionally substituted phenyl, R denotes hydrogen, halogen, alkyl with 1 to 4 carbon atoms, optionally substituted phenyl or alkoxy with 1 to 4 carbon atoms, or together with R in the o-position denotes a fused benzene ring, R denotes hydrogen, halogen, alkyl with l to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms. or together with R in the o-position denotes a fused benzene ring, R denotes hydrogen, a nitrile group. an optionally functionally modified sulpho group or an optionally functionally modified carboxyl group, R denotes hydrogen, halogen, a nitrile group, alkyl with l to 4 carbon atoms, optionally substituted phenyl. alkoxy with 1 to 4 carbon atoms, optionally functionally modified carboxyl or an optionally functionally modified sulpho group and R denotes hydrogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms.

The detergent compositions can be used for brightening textiles.

3 Claims, No Drawings 2STILBENYL-4-STYRYL-V-TRIAZOLES, THEIR USE FOR THE OPTICAL BRIGHTENING OF ORGANIC MATERIALS, AND PROCESSESFOR THEIR MANUFACTURE This is a Division of application Ser. No. 237,204, filed on Mar. 22, 1972 and now US. Pat. No. 3,862,179.

The present invention relates to the new v-triazoles, the use of these triazoles for the optical brightening of synthetic or natural organic materials, and the process for the manufacture of the compounds.

The new v-triazoles correspond to the formula wherein X denotes hydrogen, halogen, methyl or optionally substituted phenyl, R denotes hydrogen, halogen, alkyl with 1 to 4 carbon atoms, optionally substituted phenyl or alkoxy with 1 to 4 carbon atoms, or together with R in the o-position denotes a fused benzene ring, R denotes hydrogen, halogen, alkyl with l to 4 carbon atoms or alkoxy with l to 4 carbon atoms, or together with R in the o-position denotes a fused benzene ring, R denotes hydrogen, a nitrile group, an optionally functionally modified sulpho group or an optionally functionally modified carboxyl group, R, denotes hydrogen, halogen, a nitrile group, alkyl with 1 to 4 carbon atoms, optionally substituted phenyl, alkoxy with l to 4 carbon atoms, optionally functionally modified carboxyl or an optionally functionally modified sulpho group and R denotes hydrogen, alkyl with l to 4 carbon atoms or alkoxy with l to 4 carbon atoms.

The terms optionally functionally modified carboxyl and optionally functionally modified sulpho group can in general by expressed by the partial formulae COOZ and -CON(Z,Z or SO Z, SO Z and SO N(Z Z respectively; herein, Z denotes hydrogen, alkyl'with 1 to 18, preferably 1 to 4, carbon atoms, optionally substituted phenyl or benzyl, Z denotes hydrogen, alkyl with l to 6, preferably 1 to 4, carbon atoms, wherein the terminal carbon atom can be substituted by a dialkylamino group with 1 to 4 carbon atoms per alkyl part, or optionally substituted phenyl, Z denotes hydrogen, alkyl withl to 6, preferably l to 4, carbon atoms, or together with Z, and the nitrogen atom denotes a morpholino radical which is optionally substituted by alkyl with l to 4 carbon 2 atoms, and 2,, denotes alkyl with l to 4 carbon atoms or optionally substituted phenyl. Furthermore Z, in particular in the case of the sulpho group, represents an alkali metal atom, especially sodium, the ammonium group or an amine.

Preferred halogens (for the symbols X R R R and R are bromine and especially chlorine.

As alkyl radicals with l to 4 carbon atoms (for the symbols R and R tert. butyl, n-butyl, propyl, ethyl and especially methyl may be mentioned as examples.

Preferred alkyl groups with 1 to 4 carbon atoms are methyl, ethyl and tert. butyl.

Tert. butyl, ethyl, methyl, ethoxy, methoxy and chlorine are preferred as substituents for the phenyl radicals of the symbols X R R and Z.

The formula (1) for example includes the compounds of the formula wherein X denotes hydrogen or chlorine, R denotes hydrogen, chlorine, bromine, alkyl with l to 4 carbon atoms or phenyl, R denotes hydrogen, chlorine, alkyl with l to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, R denotes hydrogen, a nitrile group, an optionally functionally modified sulphonic acid group or an optionally functionally modified carboxyl group, R denotes hydrogen, chlorine, alkyl with l to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, phenyl, optionally functionally modified carboxyl or an optionally functionally modified sulpho group and R, denotes hydrogen, alkyl with l to 4 carbon atoms or alkoxy with l to 4 carbon atoms.

Preferred 2-sti1benyl-4-styrylv-triazoles correspond to the formula 11 N cn=cH- wherein X denotes hydrogen or chlorine, R denotes hydrogen, alkyl with l to 4 carbon atoms, chlorine, methoxy or phenyl, R denotes carbonamido, a nitrile group, a sulpho group or its sodium salt, SO Y,

3 4 wherein Y represents methyl, ethyl, methoxy, ethoxy, The oxidative cyclisation can be effected by the acphenoxy optionally substituted by alkyl with l to 4 cartion of the most diverse oxidising agents; at the same bon atoms or an alkylamino group with l to 4 carbon time, it is advisable to work in oxidation-resistant solatoms, wherein the terminal carbon atom can be substivents. In basic solvents, such as pyridine or pyridinetuted by a dialkylamino group with 1 or 2 carbon atoms 5 water mixtures, potassium ferricyanide can for example per alkyl part, R denotes hydrogen, chlorine, methyl, be used. The generally applicable and therefore premethoxy, phenyl, carbonmethoxy or carbethoxy and ferred process is the oxidation with cupric sulphate in R denotes hydrogen or methoxy. pyridine-water. For this, it is not necessary to use stoi- The radical R is in general in the meta-position or chiometric amounts of copper, because the monovaespecially in the para-position to the ethylene bridge. lent copper produced during the reaction can con- The compounds of the formula (1), wherein X destantly be reconverted to the divalent stage during the notes hydrogen, methyl or optionally substituted reaction by blowing in air or oxygen. The oxidation phenyl, are manufactured if one mol of water is elimiwith cupric salts, such as cupric sulphate or cupric nated under the action of an acid condensation agent, chloride, can advantageously also be carried out in and optionally with heating, from a compound of the 15 methanol or methanol/water, in the presence of ammoformula nium salts or amine salts.

pckcH-cFN-mri CH=CH a R 2 X 'C R NOH Where 1 r presents hydrogen, methyl or optionally The reduction with base metals and acids, such as Substituted phenyl and R R R R and R have the zinc dust in acetic acid or acetic acid-water mixtures, is indicated meaning. advantageously chosen for the reduction of the tria- As examples of acid condensation agents there may Zole-oxides to the triazoles in accordance with known be mentioned the h drogen halid a ids, the i anic methods. However, salts of reducing acids of sulphur or anhydrides, phosphorus pentoxide and sulphur trioxphosphorus can also be used for the reduction.

ide, the mixed inorganic-organic anhydrides, such as The route via the triazole-oxide is particularly indithe alkanoyl and aroyl, alkylsulphonyl and arylsulpho- Gated for the manufacture of compounds of the fornyl halides, for example acetyl chloride, benzoyl chlomula (1), wherein X represents halogen. The halogeride and toluenesulphochloride, as well as the purely nation and the reduction of the oxide to the end prodorganic anhydrides, such as acetic anhydride, benzoic uct can in that case be carried out in one step.

anhydride and also the mixed anhydride of formic acid The starting substances for the manufacturing proand acetic acid. cess according to the invention, or for the modified The condensation can be carried out in the presence process, can be obtained in a known manner. of organic solvents which are inert under the reaction A COmPO md 0 the formula can be manufacconditions. As such, it is possible to use high-boiling hytured, for example, by reaction of a diketone of the fordrocarbons and halogenated hydrocarbons, for exammula ple chlorobenzene, dichlorobenzene, and xylene; it is also possible to use inert slightly basic or more strongly 5 basic solvents, for example dimethylformamide, di- R methylacetamide or pyridine, picolines and quinolines. p Depending on the substituents of the oximehydrazones, R l the cyclisation can be effected by simply leaving the re- 2 action mixture to stand or by heating the reaction mixture. Possible reaction temperatures are temperatures between room temperature and 250C, preferably 100 to 150C. In some cases, the presence of basic catalysts, such as anhydrous alkali salts or alkaline earth salts of organic acids, for example sodium acetate or potassium acetate, brings favourable results as regards the yields 4 and purity of the end products. The progress of the cyc- (6) NHQNHQCH=CH 3{ wherein R R and X have the abovementioned meaning, with a compound of the formula lisation reaction can best be followed in thin layer chromatograms. The transient occurrence of O-acylated intermediate stages in the case where mixed inorganicg P t i g and l are wherein R R and R have the abovementioned mean- 0 on y mslgm cant Importance or t e Course 0 t 6 ing, and with hydroxylamine, in optional sequence, or

reaction. b

. nltros lation of, a monoketone of the formula As a modification of the process JUSt described, the y y compounds mentioned are also obtained by bringing about the cyclisation in a compound of the formula (4) R oxidatively and reducing the resulting v-triazole-l- I oxide compound with nascent hydrogen to give a com- (7) Q pound of the formula (1).

wherein R R and X, have the abovementioned meaning, and reaction of the resulting oxime of the formula with a compound of the formula (6) or by coupling of the diazotised compound of the formula wherein R R and X have the indicated meaning, and reaction of the azo compound with hydroxylamine.

The introduction of functionally modified carboxyl groups and sulpho groups (especially for R is advantageously only carried out on the triazole compound, in accordance with known methods.

The compounds according to the invention are distinguished by good compatibility with high molecular, organic substances, The new optical brighteners are suitable for the whitening of high molecular materials, such as polyolefines, for example polyethylene or polypropylene, and also polyvinyl chloride and polyacrylonitrile, but above all polyesters, especially polyesters of aromatic polycarboxylic acids with polyhydric alcohols, such as polyterephthalic acid glycol esters, synthetic polyamides, such as nylon-6 and nylon-66, and also cellulose esters, such as cellulose acetates, and alsl cellulose. Those compounds which contain groups which confer solubility in water, such as, for example, the sulphonic acid group, are especially suitable for brightening cellulose substrates.

The optical brightening of the high molecular colourless organic material is for example effected by incorporating therein small amounts of optical brighteners according to the invention, for example 0.0001 to 2%, preferably 0.0005 to 0.5%, relative to the material to be brightened, optionally together with other additives, such as plasticisers, stabilisers or pigments. The brighteners can for example be incorporated into the plastics as solutions in plasticisers, such as dioctyl phthalate, or together with stabilisers, such as dibutyl tin dilaurate or sodium pentaoctyl-tripolyphosphate, or together with pigments such as, for example, titanium dioxide. Depending on the nature of the material to be brightened, the brightener can also be dissolved in the monomers before polymerisation, in the polymer composition or, together with the polymers, in a solvent. The material pre-treated in this way is thereafter converted to the desired final shape in accordance with processes which are in themselves known, such as calendering, pressing, extrusion, spreading, casting and above all spinning and stretching. The brighteners can also be incorporated into finishes, for example into finishes for textile fibres, such as polyvinyl alcohol, orinto resins or resin precondensates such as, for example, methylol compounds of ethyleneurea, which are used for the treatment of textiles.

Preferably, colourless, high molecular organic material is also brightened in the form of fibres. A dispersion or solution of v-triazoles of the formula (1) according to the invention is advantageously used for the brightening of these fibre materials. The brightener dispersion or solution here preferably contains 0.005 to 0.5% of the v-triazole according to the invention, relative to the fibre material. In addition, the dispersion or solution can contain auxiliaries, such as dispersing agents, for example condensation products of fatty alcohols, possessing 10 to 18 carbon atoms, or alkylphenols with 15 to 25 mols of ethylene oxide, or condensation prod ucts of alkylmonoamines or polyamines possessing 16 to 18 carbon atoms with at least 10 mols of ethylene oxide, organic acids such as formic, oxalic or acetic acid, detergents, swelling agents such as dichlorobenzenes or trichlorobenzenes, wetting agents such as sulphosuccinic acid alkyl esters, bleaching agents such as sodium chlorite, peroxides or hydrosulphites and, optionally, brighteners of other categories such as, for example, derivatives of stilbene which possess affinity for cellulose.

The brightening of the fibre material with the aqueous brightener treatment bath is effected either by the exhaustion process, at temperatures of, preferably, 30 to C, or by the padding process. In the latter case, the goods are impregnated with a brightener preparation of, for example, 0.2 to 0.5% strength, and are fin-.

ished by, for example, dry or moist heat treatment, for example by steaming at 2 atmospheres or, after drying, by brief dry heating to to 220C, in the course of which the fabric is at the same time thermofixed, if appropriate. The fibre material treated in this way is finally rinsed and dried.

Colourless high molecular organic material optically brightened in accordance with the invention, especially the synthetic fibre material brightened in accordance with the exhaustion process, shows an attractive, pure white, blue-violet to bluish-tinged fluorescent appearance; material of this nature dyed in light colour shades and whitened according to the invention is distinguished by a pure colour shade.

The v-triazoles of the formula (1), according to the invention, can also be added to detergents, and the latter can be used for brightening textiles.

The content of optical brightener of the detergents is advantageously 0.001 to 0.5% by weight, relative to the solids content of the detergent.

Washing liquors which contain v-triazoles of the formula (1) according to the invention, when used for washing, imparta brilliant appearance in daylight to the textile fibres treated with the liquors, for example 7 cellulose fibres or synthetic polyamide, polyester, polyolefine and cellulose ester fibres. They can therefore in particular be used for washing these synthetic fibres or the textiles or constituents of textiles consisting of such fibres, and for washing laundry.

EXAMPLE 1 A suspension of 27.1 g of 4-hydrazino-2-cyano-sti1- benehydrochloride and 21 g of benzalisonitrosoacetone in 200 ml of methanol, 80 ml of glacial acetic acid, 80 ml of water and 20.2 g of triethylamine is stirred for 4 hours at room temperature and 6 hours at 60C. Thereafter the reaction mixture is cooled to 10C and filtered and the filtered residue is washed with methanol/water. After drying, 29.5 g, corresponding to 76.5% of theory, of hydrazone-oxime, of melting point 194 to 195C, are obtained.

A mixture of 39.2 g of the hydrazone-oxime and 29.4 g of anhydrous potassium acetate in 120 ml of dimethylformamide is warmed to 40C. 51 g of acetic anhy- 7 are obtained as a white powder of melting point 172 to 173C.

The compound thus obtained is an excellent agent for brightening plastics and synthetic fibres.

The compounds of the formula (12) listed in table I are manufactured analogously. They have similar properties to the abovementioned product.

N V2 AN Q X, @filecrt v Table 1 Formula V V V Melting point,

uncorrected. in C (13) CN H OCH 186-188 (14) CN OCH OCl-l 163 164 (15) CN 3 163-165 Table l-continued Formula V, V. V Melting point,

uncorrected. in C (16) CN H Cl 200 203 (17) CN H C,,H,, 204 205 (18) CN H COOC2H5 182 183 (19) CONH, 1-1 H 266 268 (20) -so. NHC,H 11 H 197 198 (21) so. c1-1 1-1 1-1 182 183 (23) s02CH H CH, 200 201 If instead of benzalisonitrosoacetone an equivalent amount of the isonitrosoacetone derivatives listed below, such as o-chlorobenzal-isonitrosoacetone, mchlorobenzal-isonitrosoacetone, p-chlorobenzal-isonitrosoacetone, p-methylbenzal-isonitrosoacetone, p-

Queen The 4-hydrazino-2-cyanostilbene-hydrochloride used above is obtained as follows:

A suspension of 220 g of 4-amino-2-cyanostilbene, 500 ml of water and 800 g of coarse quartz sand is vigourously stirred for 18 hours at room temperature. The fine suspension is diluted with 2,000 ml of water, the quartz sand is filtered off, 255 m1 of hydrochloric acid are added and diazotisation is carried out with 69 g of sodium nitrite in 300 ml of water at 0 to 5C. A

viscous, orange diazo suspension is produced, which is allowed to complete diazotisation for 2 hours at 5 to 8C. The diazonium salt suspension thus obtained is added dropwise, over the course of 40 minutes, to a suspension of 302 g of sodium sulphite and 24 g of sodium pyrosulphite in 700 ml of water at 20 to 25C.

9 The pH value is kept at 7.3 by adding dilute sodium hydroxide solution. An ochre-coloured suspension is produced, which is allowed to complete reaction by stirring for 30 minutes at 20 to 25C. Thereafter the reaction mixture is heated to 70C, whilst maintaining the pH value at 7.3 by adding hydrochloric acid, and is stirred for 4 hours at this temperature. The cloudy solution of the hydrazine-N-disulphonic acid is clarified and run into a mixture of 600 ml of hydrochloric acid and 200 ml of water pre-warmed to 60C, whereupon the hydrazine hydrochloride precipitates as a brownish product. The mixture is subsequently stirred for 6 hours at 70 to 75C and cooled to 20C, and the product is filtered off.

After drying, 200 g, corresponding to 74% of theory, of 4-hydrazino-2-cyanostilbene hydrochloride of melting point 195 to 197C (with decomposition) are obtained.

The hydrazine hydrochlorides of the formula listed in table 111 below are manufactured in a similar 10 fullers earth. The compound of the formula (11) is thus obtained.

If instead of the 27.1 g of 4-hydrazino-2-cyanostilbene hydrochloride equivalent amounts of the stilbenehydrazine hydrochlorides of the formulae (38) to (48) are used, and otherwise the same procedure is followed, the 2-sti1byl-4-styryl-v-triazoles of the formulae (13) to (23) are obtained.

EXAMPLE 3 39 g of 2-(2-cyanostilb-4-yl)-5-styryl-v-triazole-3- oxide, manufactured as described in the first paragraph of Example 2, in a mixture of 1,000 ml of dioxane and 200 ml of water, are brought tothe reflux temperature. On reaching the boiling point, hydrochloric acid gas is passed in for 8 hours, 300 ml of water are thereafter added and the reaction mixture is then cooled. The resulting crystalline precipitate is filtered off and washed with methanol. After three recrystallisations from chlorobenzene with the aid of fullers earth, the compound of the formula manner. CN

Table 111 Formula V V V Melting point in C (uncorrected) (38) -CN l-l OCH 176 180 w.d. (39) CN OCH,, OCH,, 204 206 w.d. (40) CN -H CH; 195 200 w.d. (41) CN H Cl 208 212 w.d. (42) CN H C H 182 183 w.d. (43) CN --H COOC H 150 1S5 w.d. (44) CONH --H --H 212 214 w.d. (45) SO NHC H -H -H 128 137 w.d. (46) SO CH H H 206 208 w.d. (47) SO C H H CH,, 184 186 w.d. (48) -SO CH H Cl-l 201 204 w.d.

w.d. with decomposition EXAMPLE 2 A suspension of 27.1 g of 4-hydrazino-2-cyanostilbene hydrochloride and 21 g of benzalisonitrosoacetone in 200 ml of methanol, 80 ml of glacial acetic acid, 80 ml of water and 20.2 g of triethylamine is stirred for 4 hours at room temperature and 6 hours at 60C. 1 1.5 g of ammonium acetate and 25.5 g of cupric chloride are now added and the mixture is boiled for a further 24 hours under reflux. Thereafter the reaction mixture is cooled to 10C and filtered, and the filter residue is washed with dilute hydrochloric acid and methanol. After drying, 37.1 g, corresponding to 95% of theory, of 2-(2-cyano-stilb-4-yl)-5styryl-v-triazole-3oxide, of melting point 190 to 193C, are obtained.

39.0 g of the triazole-oxide manufactured in this way, 26 g of zinc powder and 60 g of glacial acetic acid in 400 ml of chlorobenzene are warmed to 100C over the course of 2 hours and vigorously stirred for 24 hours at this temperature. The reaction mixture is thereafter filtered hot and the chlorobenzene is distilled off in steam. The crude v-triazole which remains is repeatedly recrystallised from chlorobenzene with the aid of are used instead of the 39 g of 2-(2-cyanostilb-4-yl)-5- styryl-v-triazole-3-oxide If instead of benzalisonitrosoacetone an equivalent amount of the isonitrosoacetone derivatives listed below, such as o-chloroben2al-isonitrosoacetone, chlorobenzalisonitrosoacetone, p-chlorobenzal-isonitrosoacetone, p-methylbenzalisonitrosoacetone, pmethoxybenzal-isonitrosoacetone or p-tert. butylbenzal-isonitrosoacetone is used, and in other respects the same procedure as described above is followed, the brighteners of the formula listed in table V below are obtained, which can be used in the same manner.

Table V Formula V V;, Melting point in C (uncorrected) (63) 4CI COOQH, 204 205 (64) 3CI COOC,H,, 160 I61 (65) 2-C1 COOC H, I80 183 (66) 4--OCH COOC H, I81 182 (67) 4--C(CH,,) -H 172 -173 (68) 4-CH H 185 -187 (69) OCHI] H 172-174 EXAMPLE 4 29 g of 4-hydrazinostilbene-2-sulphonic acid are suspended in 400 ml of water and 1 ml of approx. 40% strength sodium sulphite solution at 40C. The pH value is adjusted to by adding ammonia. A solution of 21 g of benzalisonitrosoacetone in 400 ml of methanol is rapidly added and the pH value is adjusted to 6.0 by adding acetic acid. The red-brown suspension is stirred for 20 hours at 30C and thereafter the bulk of the methanol is distilled off under reduced pressure. The mixture is now cooled to 20C and adjusted to a pH value of 2 with concentrated hydrochloric acid, and the product is filtered off, washed with 10% strength sodium chloride solution and dried in vacuo at 40C.

47 g of the oxime-hydrazone thus produced, in 700 ml of acetic anhydride, 10 g of anhydrous sodium acetate and 20 ml of dimethylformamide are heated to 104C over the course of 3 hours and stirred at this temperature for 8 hours. The mixture is then evaporated in vacuo, the residue is boiled up with ml of water and 20 ml of sodium hydroxide solution and cooled, and the product is salted out and filtered off. This salt, of the formula is then purified by repeated redissolving and reprecipitation from 5% strength sodium chloride solution and a little bleach solution, after which a yellow powder is obtained.

If instead of benzalisonitrosoacetone an equivalent amount of the isonitrosoacetone derivatives listed below, such as o-chlorobenzaI-isonitrosoacetone, mchlorobenzal-isonitrosoacetone, p-chlorobenzal-isonitrosoacetone, p-methylbenzal-isonitrosoacetone, ptert. butylbenzal-isonitrosoacetone, p-methoxybenzalisonitrosoacetone or p-phenylbenzal-isonitrosoacetone is used and in other respects the same procedure as described above is followed, the brighteners of the formula are obtained, which can be used in the same manner. V 2-Cl, 3-Cl, 4-Cl, 4-CH 4-C(CH 4-OCH or 4- C d-l EXAMPLE 44.8 g of 4-(4-styryl-v-triazole2-yl)-stilbene-2-sulphochloride are suspended in 800 ml of dry chlorobenzene and the suspension is cooled to 5C. 13.5 g of ethylamine are passed in at this temperature and thereafter the mixture is stirred for 6 hours at 10 to C and 3 hours at 130 to 135C. After adding 50 ml of a saturated sodium carbonate solution, the mixture is steam-distilled. The residue is filtered off, washed with water and dried. After repeated recrystallisation from chlorobenzene with the aid of fullers earth, 32.9 g, cor responding to 72% of theory, of the compound of the formula of melting point 197 to 198C are obtained.

If instead, of 13.5 g of ethylamine an equivalent amount of 3-dimethylamino-l-propylamine is used and otherwise the same procedure is followed, the compound of the formula is obtained. The 4-(4-styryl-v-triazole-2-yl)-stilbene-2- sulphochloride used above is obtained as follows:

205 g of 4-(4-styryl-v-triazole-2-yl)-stilbene-2-sulphonic acid (sodium salt) are introduced into 500 ml of dried chlorobenzene and the temperature is brought to 90 100C. Thereafter 188 g of phosphorus oxychloride are introduced over the course of minutes and the temperature is then raised to 130 135C, whereupon an almost clear solution is slowly produced, with evolution of hydrochloric acid gas. After 6 hours, the bulk of the chlorobenzene as well as the excess phosphorus oxychloride are distilled off under reduced pressure. After cooling, ice and water are added and the sulphonic acid chloride which has precipitated is filtered off, washed with ice water and dried.

EXAMPLE 6 22.3 g of the 4-(4-styryl-v-triazole-2-yl)-stilbene-2- sulphochloride described in Example 5 are introduced into an aqueous solution of 7.5 g of phenol and 5 g of sodium hydroxide over the course of 30 minutes at 60 to 65C and the mixture is stirred at a pH value of 9 until the reaction is completed. The crude phenol-ester of the formula is then obtained as a yellowish powder.

If the phenol is further replaced by 11.3 g of p-tert. butylphenol, the compound of the formula is obtained as a yellowish powder which is an effective brightener for the most diverse organic polymers.

EXAMPLE 7 0.2 g of Glaubers salt are added to ml of water. A solution of the optical brightener of the formula (70) is manufactured by dissolving 1 g in 1,000 mi of dimethylformamide. 2 ml of this stock solution are added to the solution described above. This aqueous solution containing the brightener is warmed to 40 45C. 3 g of a previously bleached cotton fabric are then introduced into the solution and treated for 30 minutes at this temperature. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60C.

The fabric treated in this way shows a distinct brightening effect.

EXAMPLE 8 0.06 g of alkyl-polyglycol-ether is added to 100 ml of water. A solution of an optical brightener of the formula l l is manufactured by dissolving l g in 1,000 ml of dimethylformamide. 3 ml of this stock solution are added to the solution described above. This aqueous solution or dispersion containing the brightener is warmed to 60C and 3 g of a nylon fabric are then introduced into the solution. The temperature is raised to 92 95C over the course of 10 to 15 minutes and is left thereat for 30 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60C.

The fabric treated in this way shows a distinct brightening effect.

If instead of the brightener of the formula (1 l) the same amounts of an optical brightener of the formulae (15), (l7), (19), (49), (53), (55), (58) or (70) are used, and otherwise the same procedure is followed, similar results are obtained.

EXAMPLE 9 0.12 ml of 85% strength formic acid and 0.06 g of alkyl-polyglycol-ether are added to 100 ml of water.

A solution of the optical brightener of the formula (11) is prepared by dissolving l g in 1,000 ml of dimethylformamide. 3 ml of this stock solution are added to the solution described above. This aqueous solution or dispersion containing the brightener is warmed to 60C and 3 g of polyamide fabric are then introduced into the solution. The temperature is raised to 92 95C over the course of 10 to 15 minutes and is left thereat for 30 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60C.

The fabric treated in this way shows a distinct brightening effect.

If instead of the abovementioned brightener the same amounts of optical brightener of the formulae (l5), (l7), (19), (49), (53), (54), (55), (58) or (60) are used and otherwise the same procedure is followed, similar effects are obtained.

EXAMPLE 10 0.2 g of trichlorobenzene is added to 100 ml of water.

A solution of the optical brightener of the formula (11) is prepared by dissolving l g in 1,000 ml of dimethylformamide. 1.5 ml of this stock solution are added to the solution described above. This aqueous solution containing the brightener is warmed to 60C and a polyester fabric weighing 3 g is then introduced into the solution. The temperature is raised to 95 98C over the course of 10 to 15 minutes and is left thereat for 1 hour. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for minutes at 60C.

The fabric treated in this way shows a distinct brightening effect.

If instead of the abovementioned brightener the same amounts of an optical brightener of the formula (l5), (l6), (17), (19), (49), (53), (54) or (58) are used and otherwise the same procedure is followed, similar results are obtained.

EXAMPLE 1 1 0.2 g of trichlorobenzene, 0.2 g of 80% strength sodium chlorite, 0.2 g of sodium nitrate and 0.2 g of ox- 16 alic acid or an equivalent amount of another organic or inorganic acid suitablefor this purposes are added to 100 ml of water.

A solution of the optical brightener of the formula (1 1) is prepared by dissolving l g in 1,000 ml of dimethylformamide. 1.5 ml of this stock solution are added to the solution described above. This aqueous solution containing the brightener is warmed to 60C and 3 g of a polyester fabric are then introduced into the solution. The temperature is raised to 98C over the course of 15 to 20 minutes and is left thereat for 60 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60C.

The fabric treated in this way shows a distinct brightening effect.

If instead of the abovementioned brightener the same amounts of an optical brightener of the formula (l5), (l6), (l7), (19), (49), (53), (54) or-(58) are used and otherwise the same procedure is followed, similar effects are obtained.

EXAMPLE 12 A solution of the optical brightener of the formula (11) is prepared by dissolving l g in 1,000 ml of dimethylformamide. A polyester fabric is padded with this solution (20C) (squeezing-out effect 50 to 60%, roller pressure 30 kglcm speed 3 m/minute). The fabric is subsequently fixed for 30 seconds at 200C.

The fabric treated in this way shows a distinct brightening effect.

If instead of the abovementioned brightener the same amounts of an optical brightener of the formulae (l5), (l6), (17), (18), (19), (49), (53), (55), (56) or (58) are used and otherwise the same procedure is followed, similar effects are obtained.

EXAMPLE 13 0.4 g of detergent of the following composition is added to 100 ml of water:

15.2% of dodecylbenzenesulphonate 3.8% of dodecyl alcohol sulphonate 25.6% of Na tripolyphosphate 4.8% of waterglass 1.9% of Mg silicate 5.0% of sodium carbonate 1.4% of carboxymethylcellulose 0.3% of ethylenediaminetetraacetic acid 34.4% of sodium sulphate.

A solution of the optical brightener of the formula (11) is prepared by dissolving l g in 1,000 ml of methylcellosolve. 0.8 ml of this stock solution is added to the solution described above. This aqueous dispersion containing the brightener is warmed to 55C. 5 g of a polyester fabric are then introduced into the solution and treated at this temperature for 15 minutes. After this wash, the fabric is rinsed firstly with lukewarm water and then with cold water.

The washing process described above is carried out with the same fabric, but a fresh wash liquor in each case, for a total of 15 times. A polyester fabric which shows an attractive white effect in daylight is thereby' obtained.

The fact that a good white effect is also obtained on other fibres is shown by the following:

If in the preceding example the 5 g of polyglycol terephthalate fabric are replaced by 5 g of a synthetic polyamide fabric, for example nylon, and in other respects EXAMPLE 14 0.06 g of 40% strength acetic acid and 0.06 g of alkylpolyglycol-ether are added to 100 ml of water.

A solution of the optical brightener of the formula (11) is prepared by dissolving l g in 1,000 ml of dimethylformamide. 1.5 ml of this stock solution are added to the solution described above. This aqueous dispersion containing the brightener is warmed to 60C; 3 g of a polypropylene fabric are then introduced into the solution. The temperature is raised to 95 98C over the course of to minutes and is left thereat for 30 minutes. The fabric is then rinsed for 2 minutes in running cold water and subsequently dried for minutes at 60C. The fabric treated in this way shows a distinct brighteneing effect.

If instead of the abovementioned brightener the same amounts of a brightener of the formula (15), (16), (17), (49), (53), (54) or (55) are used and otherwise the same procedure is followed, similar effects are obtained.

EXAMPLE 15 100 parts of polypropylene are homogenised with 0.5 part of titanium dioxide and 0.05 partof the optical brightener of the formula (1 1) in a kneader at 200C. The melt is spun through spinnerets under an inert gas at2 to 3 atmospheres gauge and at a temperature of 280 to 300C in accordance with known methods. The polypropylene filaments thus obtained are distinguished by a high degree of whiteness.

If instead of the abovementioned brightener the same amounts of an optical brightener of the formula (15), (17), (49), (53) or (55) are used and otherwise the same procedure is followed, similar effects are obtained.

EXAMPLE 16 In a kneader, 67 parts of polyvinyl chloride powder, 33 parts of dioctyl phthalate, 2 parts of di-n-butyldilauryldioxystannate, 0.3 part of sodium pentaoctyltripolyphosphate and 0.05 part of the optical brightener of the formula (1 l) and gelled for 15 minutes on a mixing mill at 160C and subsequently sheeted. The polyvinyl chloride sheet thus produced shows a strong fluorescence, and a brilliant white appearance, in daylight.

1 If instead of the abovementioned brightener the same amounts of an optical brightener of the formula (14), Or (59) are used and otherwise the same procedure is followed, similar effects are obtained.

EXAMPLE 17 1.000 parts of polyester granules of polyethylene glycol terephthalate are intimately mixed with 0.25 parts of the optical brightener of the formula (1 l) and then spun in a known manner under nitrogen from anextruder at a temperature of 265 to 285C through a spinneret togive filaments. The polyester filaments thus obtained show a brilliant white appearance.

If the procedure indicated above is followed but instead of the brightener of the fomiula (l 1) equivalent amounts of an optical brightener of the formula (l4), (15), (17), (18), (49), (55), (56), (64) or (68) are used and otherwise the same procedure is followed, similar results are obtained.

EXAMPLE 18 388 g of benzene-1,4-dicarboxylic acid dimethyl ester, 300 g of 1,2-ethanediol and 0.4 g of antimony oxide are heated in a stainless steel autoclave, equipped with a stirrer, a gas inlet tube, a vacuum device, a descending condenser and a heating jacket, to 200C external temperature whilst blowing pure nitrogen through the mixture, and are kept at this temperature for 3 hours. In the course thereof, the methanol slowly distils off. 0.4 g of the optical brightener of the formula l l dissolved in 40 g of 1,2-ethanediol. are now carefully introduced into the autoclave with exclusion of air, after the temperature has been allowed to drop to 190C. After completion of the addition, the temperature is raised to 285C external temperature over the course of 1 hour, whereupon 1,2-ethanediol distils off. Thereafter vacuum is applied to the autoclave, the pressure is slowly reduced to 0.2 mm Hg, and the condensation is completed under these conditions over the course of 3 hours. During this operation the mixture is thoroughly stirred.

The liquid condensation polymer is then extruded through the bottom nozzle by means of nitrogen. Monofilaments, which show a brilliant white appearance, can be manufactured from the polymer thus obtained.

Similar effects are obtained if, whilst otherwise using the same procedure, equal amounts of an optical brightener of the formula (l4), (15), (17), (18), (49), (55), (56) or (64) are used instead of the abovementioned brightener.

EXAMPLE 19 400 parts of caprolactam. 40 parts of water, 0.4 part of the brightener of the formula (11) and 1.6 parts of titanium dioxide (anatase) are mixed with one another and warmed to about 70C until the mass. liquefies. The liquid mixture is introduced into a stainless steel pressure vessel and is heated, with exclusion of oxygen, to a temperature of about 250C over the course of 1 hour, during which a pressure of 10 to 15 atmospheres is generated. After thistime, the water is distilled off and the polymeric mass is subsequently kept for 3 hours at 250C, without application of pressure, in order to degas it completely. In the course thereof, the mass reaches a viscosity which allows the polymer to be extruded in the form of strips or filaments, by means of nitrogen, through a nozzle mounted at the bottom of the pressure vessel. The solidifed polyamide is freed of monomeric constituents by extraction with water. The polyamide fibre obtained by this process is distinguished by a veryhigh degree of whiteness.

If instead of the brightener of the formula (11) the same amounts of an optical brightener of the formula (15), (32), (34), (35) or (53) are used, similar results are obtained.

EXAMPLE 20 1,000 parts of polyamide chips, obtained in a known manner from hexamethylene adipate are mixed with parts of titanium dioxide and 0.5 part of the optical brightener of the formula (1 1) in a drum for to 16 hours. The chips treated in this way are fused in an apparatus with exclusion of oxygen and stirred for a short time. Thereafter the melt is spun through spinnerets under a nitrogen atmosphere of 5 atmospheres gauge, and the product is stretched. The polyamide filaments thus obtained show a high degree of whiteness.

Similar effects are obtained if, whilst otherwise following the same procedure, equal amounts of an optical brightener of the formula (32), (34), (35) or (53) are used instead of the brightener of the formula l l We claim:

1. A detergent characterized in that it contains from 0.00l to 0.5 percent by weight of an optical brightener of the formula wherein X, denotes hydrogen, halogen, methyl or optionally substituted phenyl,

R, denotes hydrogen, halogen, alkyl with 1 to 4 carbon atoms, optionally substituted phenyl or alkoxy with l to 4 carbon atoms, or together with R in the o-position denotes a fused benzene ring,

R; denotes hydrogen, halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, or together with R in the o-position denotes a fused benzene ring,

R denotes hydrogen, a nitrile group, an optionally functionally modified sulpho group or an optionally functionally modified carboxyl group,

R denotes hydrogen, halogen, a nitrile group, alkyl with l to 4 carbon atoms, optionally substituted phenyl, alkoxy with l to 4 carbon atoms, optionally functionally modified carboxyl or an optionally functionally modified sulpho group and R denotes hydrogen, alkyl with l to 4 carbon atoms or alkoxy with l to 4 carbon atoms.

2. A detergent composition according to claim 1 wherein the optical brightener is of the formula wherein X denotes hydrogen or chlorine, R denotes hydrogen, chlorine, bromine, alkyl with l to 4 carbon atoms or phenyl, R denotes hydrogen, chlorine, alkyl with 1 to 4 carbon atoms or alkoxy with l to 4 carbon atoms, R, denotes hydrogen, a nitrile group, an optionally functionally modified sulphonic acid group or an optionally functionally modified carboxyl group, R denotes hydrogen, chlorine, alkyl with l to 4 carbon atoms, alkoxy with l to 4 carbon atoms, phenyl, optionally functionally modified carboxyl or an optionally functionally modified sulpho group and R denotes hydrogen, alkyl with l to 4 carbon atoms or alkoxy with l to 4 carbon atoms. 3. A detergent composition according to claim 1, wherein the optical brightener is of the formula v. CH=CH T. N 11 N 2 14 CH=CH R wherein X denotes hydrogen or chlorine,

21 R denotes hydrogen, alkyl with l to 4 carbon atoms,

chlorine, methoxy or phenyl, R denotes carbonamido, a nitrile group, a sulpho group or its sodium salt, SO Y, wherein Y represents methyl, ethyl, methoxy, ethoxy, phenoxy op- 5 tionally substituted by alkyl with 1 to 4 carbon atoms or an alkylamino group with 1 to 4 carbon R denotes hydrogen or methoxy. 

1. A DETERGENT CHARACTERIZED IN THAT IT CONTINS FROM 0.001 TO 0.5 PERCENT BY WEIGHT OF AN OPTOCAL BRIGHTENER OF THE FORULA
 2. A detergent composition according to claim 1 wherein the optical brightener is of the formula
 3. A detergent composition according to claim 1, wherein the optical brightener is of the formula 